Ethylbenzene disproportionation



JUE? 33 i954 D. A. McAULAY ETAL ETHYLBENZENE DIsPRoPoRTIoNATIoN Patented `luly 13, 1954 ETHYLBENZENE DISPROPORTIONATION David A. McCaulay, Chicago, Ill., and Arthur P. Lien, Highland, Ind., assignors to Standard Oil gornpany, Chicago, Ill., a corporation of Invlana Application January 30, 1952, Serial No. 269,084

6 Claims. (Cl. 260-671) This invention relates to a process for the disproportionation of ethylbenzene to produce benzene and C10 aromatic hydrocarbons. More particularly, this invention is concerned with a process for the conversion of ethylbenzene in high yields to meta-diethylbenzene.

It is well known in the art that Friedel-Crafts catalysts will activate the disproportionaton of tion at ordinary atmospheric temperatures and are able to shift the thermodynamic equilibrium, depicted above, to eect a substantially quantitative conversion or ethylbenzene into meta-diethylbenzene and benzene. This shift in the thermodynamic equilibrium can be explained upon the basis that meta-diethylbenzene selectively complexes with HF and TiF4, causing the ethylbenzene. However, it is also known that ethylbenzene disproportionation equilibriumto'be when catalysts of this type are used the equilib-0 10 shifted to the right. In more precise language rium for the reaction, the equilibrium constant for the reaction amongr 02H5 the complexed aromatics is many hundred times greater than the equilibrium constant for the 02H5 reaction among the uncomplexed aromatics. The 2 15 diethylbenzene-HF-TiF4 complex appears to con- C2H5 tain 2 mols of TiF4 and (at least) 1 mol of HF for each mol of diethylbenzene. is displaced to the left, so that when appreciable Titanium tetraluorde iS a Crystalline solid quantities of benzene are produced or present, having a boiling point of `543" F. The solid is very little diethylbenzene is formed. This is Only slightly Soluble in liquid HF. The Solubility illustrated by an experiment in which 3.0 mols 0f TF4 in liquid HF S enormously 4HOTaSEd of benzene and 1.5 mols of diethylbenzene were When dietllylbenzerle iS brought into contact with maintained at ZOB-210 F. for 3.0 hours in the the TFl, in the presence 0f liquid HF; for expresence of AlCls. The original diethylbenzene ample. a slurry 0f TiF4 and liquid HF iS rapidly was more than half converted to ethylbenzene in converted to a clear reddish liquid when the this experiment. slurry is contacted with a suiiicient amount of One object of our invention is to vprovide a diethylbenzene. process for the disproportionation of ethylben- In the ethylbenaene dSDIODOltiOIlatOIl reaction zene. Another object of our invention is to pro- We employ at least about 0.5 m01 0f TF4 Der m01 vide a process for the preparation of meta-di- 0f ethylbenzene in the Charging StOGk. If leSS ethylbenzene. Still another object of our inventhan about 1 -mol of TiF4 is used, substantially tion is to provide a process for the preparation of quantitative conversion of ythe ethylbenzene will meta-diethylbenzene wherein the catalyst funcnot be attained, so that We prefer t0 use approxitions also as a solvent for the meta-diethylbenmately 1 mol of 'IiF4 per mol of ethylbenzene rin zene. These and other objects of our invention the Charging Stock. More than 1 mol of TiF4 will become apparent from the ensuing descripper mol of ethylbenzene may be employed if detion thereof. sired, for example, as `much as 4 mols. Ingen- We have found that ethylbenzene can be diseral, the use of more than about -2 mols of Tim proportionated in the presence of liquid hydrogen per mol of ethylbenzene is undesirable because nuoride and 'rim in accordance with the follow- 40 appreciable amounts 0f triethylbenzene are ing equation: formed with a large excess of TiF4 present. The 02H5 amount of side reactants produced appears to be dependent upon the amount of undissolved 02H5 g TiF4, i. e., TiF4 which is not in the complexed 2 HFlF 45 state, in the treating zone.

. 02H5 YThe liquid used in this process should be substantially anhydrous, i. e., the HF' should and that the meta-diethylbenzene is present in Contain not more than about 1 0r 2% of water. the liquid hydrogen uorde acid phase in the Suic1ent llquld I-IFmust be present 1n the treatform of a Complex the benzene pro.. Zone 'tO participate in the OI'maIOn Of duced in the reaction and the unreacted ethylbenzene donot form acomplex with the TiFi-.HF treating agent.

Through the proper use of the Tim-liquid HF Y treating agent, wecan Qbtana very rapid reaccomplex. More than this minimum amount is desirable, particularly when an inert hydrocarbon is presentin this ,case enough liquid 'HF should be present to form a separate acid phase.

The amount of liquid HF used ymay Vary .from

3 between about 5 and about 500 volume percent based on the charging stock. However, we prefer to use between about 50 and about 300 volume percent of liquid HF.

The temperature of treatment is of considerable importance in our process because the liquid HF-'IiFi treating agent is a very powerful catalyst for reactions other than the desired ethylbenzene disproportionation. In order to avoid side reactions due to other catalytic eifects the temperature of contacting should be below about 175 F. Temperatures below 0 F. may be used when the correspondingly increased contacting time necessary to attain the desired degree of conversion can be tolerated. We prefer to carry out the disproportionation reaction at a temperature between about 50 and 125 F.

The time of Contact between the ethylbenzene and the treating agent has some effect on the degree of conversion of the ethylbenzene. The contacting time to obtain maximum conversion is dependent upon the degree of agitation and also upon the temperature of the treating zone. In general the higher the temperature the shorter the contact time. The contacting time may vary from as little as 1 minute to 6 or more hours, dependent upon the temperature in the treating zone. When operating in the preferred temperature range, i. e., from about 50 to about 125 F., the contacting time may be between about 1 minute and 30 minutes.

rIhe disproportionation reaction may be effected in the presence of inert hydrocarbons, e. g., saturated hydrocarbons, such as, butane, pentanes, hexanes, octanes, cyclopentane, methylcyclopentane, dimethylcyclopentane, hexane, methylcyclohexane, saturated naphthas and the like; these are essentially insoluble in the liquid hydrogen fluoride-Tim employed as the treating agent and as the solvent medium for the Cio aromatic hydrocarbons produced in the disproportionation of ethylbenzene. Benzene and toluene are substantially insoluble in our treating agent, the presence of complex increases the solubility of benzene and toluene in the acid phase; nevertheless, by using large amounts, these hydrocarbons may be employed as diluents. We have found that the presence of large amounts of diluent hydrocarbons has an adverse effect on the degree of conversion of the ethylbenzene. We prefer to operate Without diluent in the charging stock, i. e., we prefer to use high puritt7 ethylbenzene as the feed.

In order to illustrate the results obtainable with our process, the following examples are given. In all cases the contacting was carried out in a carbon steel reactor equipped with a 1725 R. P. M. stirrer. The experimental procedure was to add a qauntity of TiF4 to the vessel followed by liquid HF and then by the ethylbenzene feed. The contents of the vessel were stirred for a selected time, usually about minutes, at the selected temperature. At the end of the contacting time the contents of the vessel were withdrawn into a container full of cracked ice. The upper hydrocarbon layer was separated from the lower aqueous layer. The hydrocarbon layer was washed with dilute aqueous caustic to eliminate traces of HF. The hydrocarbon was carefully fractionated into narrow boiling cuts. These cuts were analyzed by the usual methods and also by ultraviolet absorption methods.

RUN 1 In this run 388 g.-3.2 mOls-of TiF4 were added to the reaction vessel; then 500 ml. of liquid HF-25 mols-were added. Finally 100 ml.- 0.8 mol-of ethylbenzene were added to the vessel. This represents 4 mols of TiF4 per mol of ethylbenzene charged. The contents in the vessel Were agitated for 30 minutes at a temperature of 63 F. The contents of the reactor were withdrawn into a vessel containing cracked ice. Under these conditions, the benzene and ethylbenzene were completely solubilized and only one liquid phase was present in the vessel. In order to recover all the material in the reaction vessel, it was necessary to Wash out the vessel with water as the excess undissolved TiF4 and hydrocarbons had adhered to the walls of the vessel. The oil was analyzed and found to consist of Composition, mol percent Benzene 34.2 Ethylbenzene 9.7 1,3-diethylbenzene 42.4 1,3,5-triethylbenzene 13.7

The diethylbenzene had inspections corresponding to those given by API project 45 data for 1,3-diethylbenzene. The ultraviolet spectrum of our product was identical with that of 1,3-diethylbenzene.

RUN 2 In this run the liquid HF and TiF4 usage was the same as that in Run 1. The ethylbenzene added amounted to 200 ml.-1.6 mols. Thus the ratio of TiF4 to ethylbenzene was 2.0. 'Ihe contents were agitated for 30 minutes at a temperature of 64 F. The vessel had to be washed out with water in order to remove undissolved TiF4 which had adhered to the walls of the vessel. The oil recovered was analyzed and found to consist of:

Composition, mol percent Benzene 31.8 Ethylbenzene 17.2 1,3-diethylbenzene 48.3 1,3,5-triethylbenzene 2.7

The comparison of the two runs shows a vefold greater amount of triethylbenzene produced in Run 1 over Run 2. It is our opinion that this large increase results from the Very large excess of TiF4 present in Run 1. We think that the hydrocarbons adsorbed on the suface of the solid TiF4 were converted to the triethylbenzene to a much greater extent than the hydrocarbons in the acid phase.

The diethylbenzene produced is substantially one isomer, namely meta-diethylbenzene, which is valuable as a pure chemical and especially valuable as a motor fuel component, as will appear from the following table from which its octane number is compared with that of ethylbenzene.

CFR-R Octane No.

Clear Blending 1,3-diethylbenzcne Isooctane-l-S cc. TEL Ethylbenzene Isooctane+0.8 cc. TEL... 124

The ligure illustrates a large scale embodiment of our process wherein the feed is a high purity ethylbenzene.

Liquid HF from source II is passed through line i2 into vessel I3, which vessel I3 is provided with agitating means not shown. Finely divided TiF4 from storage I6 is passed by Way of line I1 into vessel I3. Many methods are known in the art for introducing a iinely divided solid into a line and conveying the material into a closed vessel; e. g., storage i6 may be equipped with a star vaive at the exit thereof and line I1 may be equipped with conveying nights for propelling the solid. In vessel I3, the liquid HF and the TiF4 form a slurry-when, as is usually the case, more TiFi is used than is soluble in the liquid HF-which slurry is passed into line I3. Another method of introducing the TiFi intothe system, is to add TiCli-a liquid-into vessel I3 where the chloride reacts With HF to produce TiFli; extra HF must be added to vessel I3 to participate in the reaction. When using TiCh, vessel I3 should be provided with means for venting the HCl formed. A high purity ethylbenzene, i. e., containing less than about 5% of Xylenes, is introduced into line I9 from source 2i by Way of line 22.

In order to reduce the amount of solid TiF4 present in the system beyond line I9, and to minimize the production of triethylbenzene in this illustration, we use 1 mol of TiF4 per mol of ethylbenzene present in the feed. The amount of liquid HF added, in this illustration, is 200 volume percent, based on ethylbenzene in the feed.

The commingled stream is passed from line I8 into reactor 26 which is provided with a coil 21 and with agitating means not shown. The coil 21 is used to maintain the contents of the reactor at the desired reaction temperature, in this illustration 75 F. The reaction mixture is held for a time suicient to attain substantially complete conversion of the ethylbenzene, but not in any great excess of that time in order to avoid undesirable side reactions. A suitable reaction time at 75 F. is about 15 minutes. It is to be understood that suicient pressure must be maintained in vessel I3 and reactor 26 to keep the HF in the liquid state. From reactor 26 the materials pass through line 29, heat exchanger 3I and the line 32 into stripper 34, which stripper is equipped with heater 35. However, when operating at temperatures in the neighborhood of 125 F., it is desirable to cool quickly the reaction mixture to less than 100 F. in order to decrease the formation of undesirable by-products and cracking.

In stripper 34 the HF is removed from the reaction mixture by way of line 36 under vacuum provided by vacuum pump 31. The stripping may be facilitated by the introduction of a stripping agent, such as butane. While the stripping agent may be introduced directly into stripper 34, we prefer to utilize the stripping material as a cooling medium and therefore introduce butane from Source 4I by Way of line 42 into line 29. When a stripping agent is used, stripper 34 is operated in such a way that both the stripping agent and HF are taken overhead through line 36. The HF and butane vapors pass through line 36, vacuum pump 31, line 43, condenser 44 and line 46 into settler 48. The butane and HF are condensed in condenser 44 and the two liquids are separated in settler 48. The butane passes out of settler 48 through line 49 and is recycled to line 42 for reuse in the process. The liquid HF passes out of settler 48 through line 5I and may 6 be 'recycled to vessel I3 by Way of valved line 52 and line I2.

With the removal of the HF, the dieth-ylbenzene-TiF4 complex decomposes and the bottom of stripper 34 contains liquid hydrocarbons and solid, nely divided TiF4 precipitate. These are withdrawn from stripper 34 through valvedi line 56 and are passed into filter 51. Filter 51 may be any type of ITF-resistant and HF-vapor tighty filter, such as, a plate and frame lter, or a rotary lter. A centrifuge may be used for this separation also. We prefer to use a Sweetland-type filter. The TiF4 is retained in the lter and the liquid is passed through valved line 6I, heater 82 and line 63 into fractionator 64.

The TiF4 is removed from lter 51 by means of a backwashing operation with liquid HF from valved line 5I. The slurry ofl liquid HF and TiF4 is passed from lter 51 through valved line 66 to vessel I3 for reuse in the process. It is to be understood that even though We show only one filter, for continuous operation two or more filters would be used.

Fractionator 64 is provided with a reboiler 68'. A substantially pure benzene fraction is taken overhead from fractionator 64 through line 69 and is passed to storage not shown. A mixture of unconverted ethylbenzene, meta-diethylbenzene and triethylbenzene is withdrawn from the bottom of fractionator 64 by way of line 1I.

The contents of line 1I are passed through heater 12 and line 13 into fractionator 15, which fractionator is provided with a reboiler 16. An overhead fraction of ethylbenzene passes out of fractionator 15 through line 6I, condenser 82 and is recycled to the process by way of lines 83 and 22.

A bottoms fraction of meta-diethylbenzene and triethylbenzene is withdrawn from fractionator 15 by way of line 86. This fraction is passed through line 86, heater 81 and line 88 into fractionator 9|, which fractionator is provided with reboiler 92. Substantially pure meta-diethylbenzene is taken overhead from fractionator QI through line 94 and is passed to storage not shown. A by-product fraction of triethylbenzene and other impurities is withdrawn through line 36 and sent to storage not shown.

It is to be understood that the above described embodiment is shown for purposes of illustration only and that many other variations of our process can be readily devised by those skilled in the art.

This application is a continuation-in-part of our application Serial Number 258,918, led November 29, 1951 and entitled Refining of Hydrocarbon Oils with HF and TiFi.

We claim:

1. A process for the disproportionation of ethylbenzene to produce meta-diethylbenzene in a quantity in substantial excess of the thermodynamic equilibrium quantity, which process comprises contacting ethylbenzene in the absence of other reactive hydrocarbons with at least about 5 volume percent of liquid hydrovolume percent of liquid hydrogen fluoride and with at least about 0.5 mol of TiF4 per mol of ethylbenzene at a temperature between about F. and about 175 F. under a pressure sufficient at least to maintain a liquid phase, withdrawing at least a portion of the reaction mixture to a settling zone, withdrawing from said settling zone a solution comprising hydrogen uoride, TiF4 and meta-diethylbenzene, and recovering said metadiethylbenzene from said solution.

3. The process of claim 2 wherein at least about 1 mol of TiF4 is maintained in the reaction zone per mol of ethylbenzene charged.

4. A process for the disproportionation of ethylbenzene which comprises contacting ethylbenzene in the absence of other reactive hydrocarbons in a reaction zone with at least about 5 volume percent of liquid hydrogen uoride and with at least about 0.5 mol of TiF4 per mol of ethylbenzene at a temperature between about 0 F. and about 175 F. under a pressure suicient at least to maintain a liquid phase and separating meta-diethylbenzene from the reaction products.

5. The process of claim 4 wherein at least about 1 mol of TiF4 is maintained in the reaction zone per mol of ethylbenzene charged and the reaction temperature is between about F. and about F.

6. A process for the substantially quantitative disproportionation of ethylbenzene to produce benzene and meta-diethylbenzene to the substantial exclusion of other diethylbenzenes, which process comprises contacting ethylbenzene in the absence of other reactive hydrocarbons, with between about 50 and about 300 volume percent of liquid hydrogen fluoride and with between about 1 to 2 mols of TiF4 per mol of ethylbenzene at a temperature between 50 and 125 F. under a pressure suicient at least to maintain a liquid phase, allowing at least a portion of the reaction mixture to settle in a settling zone, withdrawing from said settling zone a liquid IdF-rich phase and recovering meta-diethylbenzene from said phase.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 2,425,559 Passino Aug. 12, 1947 2,514,866 Hovey July 11, 1950 2,528,893 Lien et al Nov. '7, 1950 

1. A PROCESS FOR THE DISPROPORTIONATION OF ETHYLBENZENE TO PRODUCE META-DIETHYLBENZENE IN A QUANTITY IN SUBSTANTIAL EXCESS OF THE TERMODYNAMIC EQUILIBRIUM QUANTITY, WHICH PROCESS COMPRISES CONTACTING ETHYLBENZENE IN THE ABSENCE OF OTHER REACTIVE HYDROCARBONS WITH AT LEAST ABOUT 5 VOLUME PERCENT OF LIQUID HYDROGEN FLUORIDE AND WITH AT LEAST ABOUT 0.5 MOL OF TIF4 PER MOL OF ETHYLBENZENE AT A TEMPERATURE BETWEE ABOUT 0* F. AND ABOUT 175* F. UNDER A PRESSURE SUFFICIENT AT LEAST TO MAINTAIN A LIQUID PHASE AND SEPARATING META-DIETHYLBENZENE FROM THE REACTION PRODUCTS. 